Photoprotective cosmetic compositions containing aromatic amide, sulphonamide or carbamate derivatives of acrylonitrile and novel aromatic amide, sulphonamide or carbamate derivatives of acrylonitrile

ABSTRACT

Cosmetic compositions for topical use for protecting the skin and the hair, containing, in a cosmetically acceptable support, at least one compound of formula (1) or (2)  
                 
 
     in which X 1  represents R 3 —(C═O)—, R 3 —SO 2 — or R 3 —O—(C═O)—, X 2  represents —(C═O)—R′ 3 —(C═O)—, —SO 2 —R′ 3 —SO 2 — or —(C═O)—O—R′ 3 —O—(C═O)—, Y represents —(C═O)—R 4  or —SO 2 R 5 ,  
     R 2  represents a C 1-8  alkyl group, n is 0, 1 or 2, R 3  represents C 1-30  alkyl or C 3-30  alkenyl, R′ 3  represents a single bond or a divalent C 1-30  alkylene or C 3-30  alkenylene radical, R 4  represents —OR 6  or —NHR 6 , R 5  represents C 1-30  alkyl or a phenyl nucleus, R 6  represents C 1-30  alkyl or C 3-30  alkenyl, and novel compounds of formula (2)

[0001] The present invention relates to cosmetic compositions fortopical use, in particular intended for photo-protecting the skin and/orthe hair, comprising an effective amount of at least one aromatic amide,sulphonamide or carbamate derivative of acrylonitrile, to novel aromaticamide, sulphonamide or carbamate derivatives of acrylonitrile and to anon-therapeutic process for treating the skin using these compositions.

[0002] It is known that radiation with wavelengths of between 280 nm and400 nm permit tanning of the human epidermis and that radiation withwavelengths of between 280 and 320 nm, known as UV-B radiation, causeskin burns and erythema that may be harmful to the development of anatural tan. For these reasons, and also for aesthetic reasons, there isincreasing demand for means for controlling this natural tanning. ThisUV-B radiation should thus be screened out.

[0003] It is also known that UV-A rays, with wavelengths of between 320and 400 nm, which cause tanning of the skin, are liable to induceadverse changes therein, especially in the case of sensitive skin and/orskin that is continually exposed to solar radiation. In particular, UV-Arays bring about a loss of elasticity of the skin and the appearance ofwrinkles, leading to premature ageing of the skin. They promote theonset of the erythemal reaction or amplify this reaction in certainindividuals and may even be the cause of phototoxic or photoallergicreactions. Thus, for aesthetic and cosmetic reasons such as maintenanceof the natural elasticity of the skin, an increasingly large number ofpeople wish to control the effect of UV-A rays on their skin. It is thusdesirable also to screen out UV-A radiation.

[0004] UV-A rays are divided into UV-A-1 rays known as “long WV-A” withwavelengths of between 340 and 400 nm, and UV-A-2 rays known as “shortUV-A” with wavelengths of between 320 and 340 nm. A good LTV-A screeningagent should cover these two ranges of wavelengths as much as possible,i.e. it should be a broad UV-A screening agent, without, however, havingan intrinsic coloration due to the absorption of light at wavelengths inthe visible range. Specifically, an important problem associated withthe cosmetic use of coloured screening agents is the staining of fabricsliable to come into contact with these screening agents, such as towelsand clothing.

[0005] Many compounds intended for protecting the skin against UV-Aand/or UV-B radiation have been proposed to date.

[0006] Most of these are aromatic compounds that absorb UV radiation inthe region between 280 nm and 315 nm, or in the region between 315 nmand 400 nm and above, or alternatively in both these regions. They areusually formulated in antisun compositions that are in the form ofoil-in-water emulsions, the lipophilic or hydrophilic organic screeningagents being present in dissolved form, in one or other of these phases,in amounts that are suitable to obtain the desired sun protection factor(SPF).

[0007] The expression “sun protection factor” means the ratio of theirradiation time required to reach the erythema-forming threshold in thepresence of the test screening agent to the irradiation time required toreach this same threshold in the absence of screening agent.

[0008] Besides their screening power on solar radiation, photoprotectivecompounds must also have good cosmetic properties, good resistance towater and perspiration (remanence) and also satisfactory photostability.

[0009] Among all the aromatic compounds derived from 2-cyano-acrylicacid that have been proposed for this purpose, mention may be made ofthe compounds described in patent FR 1 368 808, international patentapplications WO 99/36049 and WO 97/15279, and those described inEuropean patent applications EP-A-0 911 020, EP-A-0 716 089 and EP-A-0005 182. However, none of these screening agents simultaneouslysatisfies the three conditions of being a broad UV screening agent, thatis to say of screening out both long UV-A and short UV-A, and of beinguncoloured and photostable.

[0010] Mention may also be made of4-(tert-butyl)-4′-methoxy-dibenzoylmethane, sold under the trade nameParsol® 1789 by the company Hoffman Laroche, which is an uncoloured longUV-A screening agent with a broad spectrum of absorption in the UV-Arange, but which has the major drawback of degrading under the effect ofsolar radiation, that is to say of not being photostable.

[0011] The Applicant has discovered, surprisingly, that a particularfamily of aromatic amide, sulphonamide or carbamate derivatives ofacrylonitrile have, simultaneously:

[0012] a broad spectrum of UV-A absorption, while at the same time beinglong UV-A screening agents,

[0013] an absence of coloration,

[0014] satisfactory photostability, and

[0015] good cosmetic properties,

[0016] and thus constitute excellent sunscreens that may be used, inreplacement for Parsol® 1789, in cosmetic compositions, in particular toprotect the skin and the hair against the harmful effects of sunlight.

[0017] One subject of the present invention is, consequently, a cosmeticcomposition for topical use, in particular intended for photoprotectingthe skin and/or the hair, containing, in a cosmetically acceptablesupport, at least one compound chosen from the aromatic amide,sulphonamide or carbamate derivatives of acrylonitrile of formula (1)below or the corresponding dimers of formula (2) below.

[0018] A subject of the present invention is also the novel compounds offormula (2) below.

[0019] Finally, a subject of the present invention is a non-therapeuticprocess for protecting the skin and/or the hair against solar radiation,which consists in applying to the skin and/or the hair an effectiveamount of the cosmetic composition defined above.

[0020] The aromatic amide, sulphonamide or carbamate derivatives ofacrylonitrile used as broad-spectrum UV-A screening agents in thecosmetic compositions of the present invention are compoundscorresponding to the general formula (1)

[0021] or dimers of such compounds, corresponding to formula (2):

[0022] in which

[0023] X₁ represents a radical R₃—(C═O)—, R₃—SO₂— or R₃—O—(C═O)—,

[0024] X₂ represents a divalent radical of formula —(C═O)—R′₃—(C═O)—,—SO₂—R′₃—SO₂— or —(C═O)—O—R′₃—O—(C═O)—,

[0025] Y represents a radical —(C═O)—R₄ or —SO₂R₅,

[0026] R₂ represents a linear or branched C₁₋₈ alkyl group,

[0027] n is 0, 1 or 2,

[0028] R₃ represents a linear or branched C₁₋₃₀ alkyl or C₃₋₃₀ alkenylradical, possibly bearing one or more hydroxyl substituents and possiblycontaining, in the carbon chain, one or more hetero atoms chosen fromoxygen, nitrogen and silicon atoms,

[0029] R′₃ represents a single bond or a linear or branched divalentC₁₋₃₀ alkylene or C₃₋₃₀ alkenylene radical, possibly bearing one or morehydroxyl substituents and possibly containing, in the carbon chain, oneor more hetero atoms chosen from oxygen, nitrogen and silicon atoms,

[0030] R₄ represents a radical —OR₆ or —NHR₆,

[0031] R₅ represents a linear or branched C₁₋₃₀ alkyl radical or aphenyl nucleus that is unsubstituted or substituted with C₁₋₄ alkyl oralkoxy radicals,

[0032] R₆ represents a linear or branched C₁₋₃₀ alkyl or C₃₋₃₀ alkenylradical, possibly bearing one or more hydroxyl substituents and possiblycontaining, in the carbon chain, one or more hetero atoms chosen fromoxygen, nitrogen and silicon atoms.

[0033] Although, in formula (1) above, only the isomers in which thecyano substituent is in the cis position relative to thepara-aminophenyl substituent have been represented, this formula shouldbe understood as also encompassing the corresponding trans isomer. Thisis likewise the case for formula (2) in which, for each of the twodouble bonds, and independently, the cyano and para-aminophenylsubstituents may be in a cis or trans configuration relative to eachother.

[0034] The compounds of formula (2) above are novel compounds.

[0035] As mentioned above, the compounds of formulae (1) and (2) haveexcellent screening power in the broad UV-A range, i.e. in thewavelength range from 320 nm to 400 nm, show satisfactory photostabilityand are substantially colourless.

[0036] Among the compounds of formulae (1) and (2) that are particularlypreferred are those in which:

[0037] X₁ represents a radical R₃—(C═O)— or R₃—O—(C═O)—,

[0038] X₂ represents a radical —(C═O)—CH₂—CH₂—(C═O)—,

[0039] Y represents a radical —(C═O)—R₄,

[0040] n is 0,

[0041] R₃ represents a linear or branched C₁₋₁₀ alkyl radical,

[0042] R₄ represents a radical —O—R₆, and

[0043] R₆ represents a linear or branched C₁₋₃₀ alkyl group optionallycontaining one or more silicon atoms.

[0044] The derivatives of formulae (1) and (2) may be prepared accordingto known methods.

[0045] To prepare the derivatives of formula (1), 1 mol of a derivativeof formula (3) may be reacted with 1 mol of an acyl chloride, asulphonyl chloride or a chloroformate of formula (4) in the presence ofsolvent and of a hydrochloric acid trapping agent, according to thefollowing reaction scheme:

[0046] Y, R₂, R₃ and n having the meanings given above for formula (1).The derivative of formula (3) may be prepared by coupling a compound offormula (5) below with a cyano derivative of formula (6) below accordingto the reaction scheme:

[0047] in which R₂, Y and n have the meanings given above.

[0048] The compound of formula (1) may also be prepared by coupling acompound of formula (7) below with a cyano derivative of formula (6)below according to the following reaction scheme:

[0049] in which Y, R₂, X and n have the meanings given above; thederivative (7) may be prepared by coupling a derivative of formula (5)below with an acyl chloride, a sulphonyl chloride or a chloroformate offormula (4) below in the presence of a solvent and of a hydrochloricacid trapping agent, according to the following reaction scheme:

[0050] in which R₂, R₃ and n have the meanings given above.

[0051] To prepare the derivatives of formula (2), two moles of aderivative of formula (3), prepared in the manner described above, maybe reacted with one mole of a dicarboxylic or disulphonic aciddichloride or a dichloroformate of formula (8) below in the presence ofa solvent and of a hydrochloric acid trapping agent, according to thefollowing reaction scheme:

[0052] in which Y, R₂, R′₃ and n have the meanings given above.

[0053] The compounds of formula (2) may also be prepared by coupling onemole of a derivative of formula (9) below with two moles of a cyanoderivative of formula (6) below:

[0054] in which Y, R₂, R′₃ and n have the meanings given above.

[0055] The derivative of formula (9) may be prepared by coupling twomoles of a derivative of formula (5) below with one mole of adicarboxylic or disulphonic acid dichloride or a dichloroformate offormula (8) below in the presence of a solvent and of a hydrochloricacid trapping agent, according to the following reaction scheme:

[0056] in which R₂, R′₃ and n have the meanings given above.

[0057] The compound(s) of formula (1) or (2) is(are) preferably presentin the cosmetic compositions for topical use of the present invention ina proportion of 0.1% and 20% by weight and in particular in a proportionof from 0.5% to 10% by weight, relative to the total weight of thecosmetic composition.

[0058] The cosmetic compositions, in particular the antisuncompositions, of the present invention can also contain one or moreorganic sunscreens that are active in the UV-A and/or UV-B range, otherthan the broad-spectrum UV-A screening agents of formula (1) or (2)described above.

[0059] These sunscreens may be chosen especially from cinnamicderivatives, salicylic derivatives, benzylidenecamphor derivatives,triazine derivatives such as those described in the patents or patentapplications U.S. Pat. No.4,367,390, EP 0 863 145, EP 0 517 104, EP 0570 838, EP 0 796 851, EP 0 775 698, EP 0 878 469, EP 0 933 376 and EP 0893 119, benzophenone derivatives, β,β′-di-phenylacrylate derivatives,phenylbenzimidazole derivatives, anthranilic derivatives, imidazolinederivatives, methylenebis(hydroxyphenylbenzotriazole) derivatives suchas those described in the patents or patent applications U.S. Pat. No.5,237,071, U.S. Pat. No. 5,166,355, GB 2 303 549, DE 19726184 and EP 0893 119, p-aminobenzoic acid derivatives, and screening hydrocarbonpolymers and screening silicones such as those described especially inpatent application WO 93/04665.

[0060] Examples of such additional UV-A-active and/or UV-B-activesunscreens that may be mentioned include the following compounds,denoted by their NCI name, and also mixtures thereof:

[0061] Para-Aminobenzoic Acid Derivatives:

[0062] PABA

[0063] ethyl PABA

[0064] ethyl dihydroxypropyl PABA

[0065] ethylhexyl dimethyl PABA sold especially under the trade nameEscalol® 507 by ISP,

[0066] glyceryl PABA,

[0067] PEG-25 PABA sold under the trade name Uvinul® p25 by BASF,

[0068] Salicylic Derivatives:

[0069] homosalate sold under the trade name Eusolex® HMS by Rona/EMIndustries,

[0070] ethylhexyl salicylate sold under the trade name Neo Heliopan® OSby Haarmann & Reimer,

[0071] dipropylene glycol salicylate sold under the trade name Dipsal®by Scher,

[0072] TEA salicylate sold under the trade name Neo Heliopan® TS byHaarmann & Reimer,

[0073] Cinnamic Derivatives:

[0074] ethylhexyl methoxycinnamate sold especially under the trade nameParsol® MCX by Hoffmann Laroche,

[0075] isopropyl methoxycinnamate

[0076] isoamyl methoxycinnamate sold under the trade name Neo Heliopan®E 1000 by Haarmann & Reimer,

[0077] cinoxate,

[0078] DEA methoxycinnamate,

[0079] diisopropyl methylcinnamate,

[0080] glyceryl ethylhexanoate dimethoxycinnamate

[0081] β,β-Diphenylacrylate Derivatives:

[0082] octocrylene sold especially under the trade name Uvinul® 539 byBASF,

[0083] etocrylene sold especially under the trade name Uvinul® N-35 byBASF,

[0084] Benzophenone Derivatives:

[0085] benzophenone-1 sold under the trade name Uvinul® 400 by BASF,

[0086] benzophenone-2 sold under the trade name Uvinul® D-50 by BASF,

[0087] benzophenone-3 or oxybenzone sold under the trade name Uvinul®M-40 by BASF,

[0088] benzophenone-4 sold under the trade name Uvinul® MS-40 by BASF,

[0089] benzophenone-5,

[0090] benzophenone-6 sold under the trade name Helisorb® 11 by Norquay,

[0091] benzophenone-8 sold under the trade name Spectrasorb® UV-24 byAmerican Cyanamid

[0092] benzophenone-9 sold under the trade name Uvinul® DS-49 by BASF,

[0093] benzophenone-12

[0094] Benzylidenecamphor Derivatives:

[0095] 3-benzylidenecamphor manufactured under the name Mexoryl® SD byChimex,

[0096] 4-methylbenzylidenecamphor sold especially under the trade nameEusolex® 6300 by Merck,

[0097] benzylidenecamphorsulphonic acid manufactured under the nameMexoryl® SL by Chimex,

[0098] camphorbenzalkoniummethosulphate manufactured under the nameMexoryl® SO by Chimex,

[0099] terephthalylidenedicamphorsulphonic acid manufactured under thename Mexoryl® SX by Chimex,

[0100] polyacrylamidomethylbenzylidenecamphor manufactured under thename Mexoryl® SW by Chimex,

[0101] Phenylbenzimidazole Derivatives:

[0102] phenylbenzimidazolesulphonic acid sold especially under the tradename Eusolex® 232 by Merck

[0103] benzimidazilate sold under the trade name Neo Heliopan® AP byHaarmann & Reimer

[0104] Triazine Derivatives:

[0105] anisotriazine sold under the trade name Tinosorb® S by CibaGeigy,

[0106] ethylhexyltriazone sold especially under the trade name Uvinul®T150 by BASF,

[0107] diethylhexylbutamidotriazone sold under the trade name Uvasorb®HEB by Sigma 3V,

[0108] Phenylbenzotriazole Derivatives:

[0109] drometrizole trisiloxane sold under the trade name Silatrizole®by Rhodia Chimie,

[0110] methylenebis(benzotriazolyl)tetramethylbutylphenol sold in solidform under the trade name Mixxim® BB/100 by Fairmount Chemical or inmicronized form as an aqueous dispersion under the trade name Tinosorb®M by Ciba Speciality Chemicals,

[0111] Anthranilic Derivatives:

[0112] menthylanthranilate sold under the trade name Neo Heliopan® MA byHaarmann & Reimer,

[0113] Imidazoline Derivatives:

[0114] ethylhexyl dimethoxybenzylidene dioxoimidazoline propionate

[0115] Benzalmalonate Derivatives:

[0116] polyorganosiloxane containing benzalmalonate functions, soldunder the trade name Parsol® SLX by Hoffmann Laroche

[0117] The organic UV screening agents that are more particularlypreferred are chosen from the following compounds:

[0118] ethylhexyl salicylate,

[0119] ethylhexyl methoxycinnamate,

[0120] octocrylene,

[0121] phenylbenzimidazolesulphonic acid,

[0122] terephthalylidenedicamphorsulphonic acid,

[0123] benzophenone-3,

[0124] benzophenone-4,

[0125] benzophenone-5,

[0126] 4-methylbenzylidenecamphor,

[0127] benzimidazilate,

[0128] anisotriazine,

[0129] ethylhexyltriazone,

[0130] diethylhexylbutamidotriazone,

[0131] methylenebis(benzotriazolyl)tetramethylbutylphenol,

[0132] drometrizoletrisiloxane,

[0133] and mixtures thereof.

[0134] The cosmetic compositions according to the invention may alsocontain agents for artificially tanning and/or browning the skin(self-tanning agents) such as dihydroxyacetone (DHA).

[0135] The cosmetic compositions according to the invention may alsocontain one or more mineral pigments and in particular metal oxidenanopigments, that are coated or uncoated, such as, for example,nanopigments of titanium oxide in amorphous or crystallized (rutileand/or anatase) form, of iron oxide, of zinc oxide, of zirconium oxideor of cerium oxide. These nanopigments have a mean particle size ofbetween 5 nm and 100 nm and preferably between 10 nm and 50 nm and areall known UV photoprotective agents.

[0136] These nanopigments may be coated with known coating agents suchas, for example, alumina and/or aluminium stearate.

[0137] Such coated or uncoated nanopigments are described, for example,in patent applications EP-A-0 518 772 and EP-A-0 518 773.

[0138] The cosmetic compositions may also contain adjuvants usually usedin cosmetics, such as fatty substances, organic solvents, silicones,surfactants, anionic, cationic, nonionic or amphoteric polymers ormixtures thereof, thickeners, antioxidants, opacifiers, stabilizers,antifoams, fragrances, preserving agents, fillers, sequestering agents,propellants, pH regulators and colorants, and mixtures thereof.

[0139] They may also contain one or more cosmetic active principleschosen, for example, from softeners, hydroxy acids, vitamins,moisturizers, emollients, free-radical scavengers, substance Pantagonists and anti-inflammatories, and mixtures of these compounds.

[0140] The fatty substances may consist of an oil or a wax or mixturesthereof, and they also comprise fatty acids, fatty alcohols and fattyacid esters. The oils may be chosen from animal, plant, mineral orsynthetic oils and especially from hydrogenated palm oil, hydrogenatedcastor oil, liquid petroleum jelly, liquid paraffin, purcellin oil,volatile or non-volatile silicone oils, isoparaffins, polyolefins,fluoro oils and perfluoro oils. Similarly, the waxes may be chosen fromanimal, fossil, plant, mineral and synthetic waxes that are known perse, for instance petroleum jelly, paraffin, lanolin, hydrogenatedlanolin and acetylated lanolin.

[0141] Among the organic solvents that may be mentioned are loweralcohols and polyols such as ethanol, isopropanol, propylene glycol,glycerol and sorbitol.

[0142] The thickeners may be chosen especially from modified orunmodified guar gums and cellulose gums, such as hydroxypropyl guar gum,methylhydroxyethylcellulose, hydroxypropylmethylcellulose orhydroxyethylcellulose.

[0143] Needless to say, a person skilled in the art will take care toselect this or these optional additional compound(s) and/or the amountsthereof such that the advantageous properties intrinsic to the compoundsand compositions according to the invention are not adversely affectedby the envisaged addition(s).

[0144] The cosmetic compositions for topical use of the invention may beprepared according to techniques that are well known to those skilled inthe art, in particular those intended for preparing emulsions ofoil-in-water or water-in-oil type.

[0145] These compositions may be in particular in the form of a lotion,a thickened lotion, a simple or complex emulsion (O/W, W/O, O/W/O orW/O/W emulsion), such as a cream or a milk, in the form of a gel orcream-gel, or in the form of a powder or a solid tube, and mayoptionally be packaged as an aerosol and may be in the form of a mousseor a spray.

[0146] When it is an emulsion, the aqueous phase of this emulsion maycomprise a nonionic vesicular dispersion prepared according to knownprocesses (Bangham, Standish and Watkins, J. Mol. Biol. 13, 238 (1965) ,FR 2 315 991 and FR 2 416 008).

[0147] The cosmetic composition of the invention may be used as acomposition for protecting the human epidermis or the hair againstultraviolet rays, as an antisun composition or as a makeup product.

[0148] When the cosmetic composition according to the invention is usedfor protecting the human epidermis against UV rays or as an antisuncomposition, it may be in the form of a lotion, a suspension or adispersion in solvents or fatty substances, in the form of a nonionicvesicular dispersion or in the form of an emulsion, preferablyoil-in-water type, such as a cream or a milk, or in the form of anointment, a gel, a cream-gel, a solid tube, an aerosol mousse or aspray.

[0149] When the cosmetic composition according to the invention is usedfor protecting the hair against UV rays, it may be in the form of ashampoo, a lotion, a gel, a rinse-out composition, to be applied beforeor after shampooing, before or after dyeing or bleaching, or before,during or after permanent-waving or straightening the hair, a styling ortreating lotion or gel, a lotion or gel for blow-drying or hairsetting,a permanent-waving, straightening, dyeing or bleaching composition forthe hair or a hair lacquer.

[0150] When the composition is used as a makeup product for theeyelashes, the eyebrows, the skin or the hair, such as an epidermaltreatment cream, a foundation, a tube of lipstick, an eyeshadow, a facepowder, a mascara, an eyeliner or a colouring gel, it may be in solid orpasty, anhydrous or aqueous form, for instance an oil-in-water orwater-in-oil emulsion, a suspension or a gel.

[0151] As a guide, for the antisun formulations in accordance with theinvention, which contain a support of oil-in-water emulsion type, theaqueous phase generally represents from 50% to 95% by weight andpreferably from 70% to 90% by weight, relative to the total formulation,the oily phase from 5% to 50% by weight and preferably from 10% to 30%by weight, relative to the total formulation, and the (co)emulsifier(s)from 0.5% to 20% by weight and preferably from 2% to 10% by weight,relative to the total formulation.

[0152] The examples that follow illustrate the invention

EXAMPLE 1

[0153]

[0154] a) Preparation of ethyl 3-(4-aminophenyl)-2-cyanoacrylate

[0155] 36 g (0.3 mol) of para-aminobenzaldehyde are suspended in 300 mlof ethanol. 33.9 g (0.3 mol) of ethyl cyanoacetate and a mixture of0.375 ml of diethylamine and 1.125 ml of acetic acid, as catalyst, areadded to the suspension. The reaction mixture is refluxed for 2 hours,left to cool and then crystallized. After separating out the crystals byfiltration and drying, 53.9 g (83% yield) of ethyl3-(4-aminophenyl)-2-cyanoacrylate are obtained in the form oforange-coloured crystals.

[0156] b) Preparation of ethyl2-cyano-3-(4-decanoylamino-phenyl)acrylate

[0157] 21.6 g (0.1 mol) of the compound synthesized in step a) aredissolved in 300 ml of tetrahydrofuran. 19 g (0.1 mol) of decanoylchloride are added dropwise at a temperature of 30° C. Gradualthickening of the reaction medium is observed. 10.1 g (0.1 mol) oftriethylamine are then added, which is reflected by a temperatureincrease to 40° C. Stirring is continued for 30 minutes and the reactionmixture is then poured into 500 ml of water. The precipitate obtained isseparated out by filtration, washed with water, recrystallized fromethanol and dried. 33.5 g (84% yield) of pale-yellow coloured crystalsof ethyl 2-cyano-3-(4-decanoylaminophenyl)acrylate are thus obtained.

[0158] Melting point: 76° C.

[0159] UV absorption (as a solution in ethanol):

[0160] λ_(max)=350 nm, ε_(max)=30 380, EI %=820

[0161] Elemental analysis for C₂₂H₃₀N₂O₃

[0162] calculated: C 71.32; H 8.16; N 7.56; O 12.96

[0163] found: C 71.43; H 8.26; N 7.69; O 13.03

EXAMPLE 2

[0164]

[0165] a) Preparation of 2-ethylhexyl3-(4-acetylaminophenyl)-2-cyanoacrylate

[0166] A mixture of 35 g (0.18 mol) of 2-ethylhexyl cyanoacetate and 30g (0.18 mol) of 4-acetamidobenzaldehyde in 300 ml of isopropanol isrefluxed for 3 hours. The reaction mixture is then allowed to cool andis crystallized. The crystals formed are separated out by filtration andare recrystallized from a minimum amount of isopropanol. Afterfiltration and drying, 33.3 g (54% yield) of 2-ethylhexyl3-(4-acetylaminophenyl)-2-cyanoacrylate are obtained in the form of apale yellow powder.

[0167] Melting point: 119° C.

[0168] UW absorption (as a solution in ethanol):

[0169] λ_(max)=351 nm, ε_(max)=30 960, EI %=904

[0170] Elemental analysis for C₂₀H₂₆N₂O₃

[0171] calculated: C 70.15; H 7.65; N 8.18; O 14.02

[0172] found: C 70.08; H 7.65; N 8.16; O 14.03

EXAMPLE 3

[0173]

[0174] a) Preparation of3-(4-aminophenyl)-2-methanesulphonyl-acrylonitrile

[0175] A mixture of 11.9 g (0.1 mol) of methanesulphonyl-acetonitrile,12 g (0.1 mol) of 4-aminobenzaldehyde and a catalyst consisting of 0.125ml of diethylamine and 0.375 ml of acetic acid in 150 ml of ethanol isrefluxed for 6 hours. After stopping the reaction, the insolublematerials are removed by hot filtration and the filtrate is concentratedunder vacuum, left to cool and crystallized. After filtering off anddrying the crystals, 11.6 g (52% yield) of an orange-coloured powder of3-(4-aminophenyl)-2-methanesulphonylacrylonitrile are obtained.

[0176] b) Preparation of3-[4-(2-ethylhexanoyl)aminophenyl]-2-methanesulphonylacrylonitrile

[0177] 4 g (0.018 mol) of the compound obtained in step a) are suspendedin 50 ml of tetrahydrofuran. 2.9 g (0.018 mol) of 2-ethylhexanoylchloride are added dropwise at room temperature, which results in atemperature increase to 27° C. The mixture is heated to 45° C. and 1.8 g(0.018 mol) of triethylamine are then added. The resulting mixture isreacted for 1 hour at 60° C. 150 ml of water are then added and themixture is left to crystallize. The precipitate is separated out byfiltration, washed with water and suction-filtered. The product isrecrystallized from an isopropanol/water mixture. 3.9 g (62% yield) of apale yellow powder of the desired compound are thus obtained.

[0178] Melting point: 178° C.

[0179] UV absorption (as a solution in ethanol):

[0180] λ_(max)=348 nm, ε_(max)=33 500, EI %=960

[0181] Elemental analysis for C₁₈H₂₄N₂O₃S

[0182] calculated: C 62.04; H 6.94; N 8.04; O 13.77; S 9.20

[0183] found: C 61.90; H 6.88; N 8.05; O 13.77; S 9.13

EXAMPLE 4

[0184]

[0185] a) Preparation of 2-ethylhexyl 3-(4-aminophenyl)-2-cyanoacrylate

[0186] 36.3 g (0.3 mol) of p-aminobenzaldehyde are suspended in 450 mlof isopropanol. A mixture of 59.1 g (0.3 mol) of 2-ethylhexylcyanoacetate and of catalyst (0.375 ml of diethylamine and 1.125 ml ofacetic acid) is introduced therein. The mixture is refluxed for 5 hours.The same amount of catalyst is added again and refluxing is continuedfor a further 4 hours. The insoluble materials are removed by hotfiltration and the mixture is concentrated to a volume of 300 ml andleft to crystalize. After filtration and drying, 59.6 g (66% yield) ofan orange-coloured powder are obtained, and are used without furtherpurification for the following step.

[0187] b) Preparation of 2-ethylhexyl2-cyano-3-[4-(3,3-di-methyl)butyrylamino)phenyl]acrylate

[0188] 10 9 (0.033 mol) of 2-ethylhexyl3-(4-aminophenyl)-2-cyanoacrylate are dissolved in 50 ml oftetrahydro-furan. 4.48 g (0.033 mol) of tert-butylacetyl chloride areadded dropwise at room temperature, resulting in a temperature increaseto 29° C. The mixture is heated to about 45° C. and 3.3 g (0.033 mol) oftriethylamine are then added. The resulting mixture is heated at 50° C.for 30 minutes. After cooling to room temperature, 150 ml of water areadded and the resulting mixture is extracted with dichloromethane. Theorganic phase is washed with water, dried and concentrated under vacuum.After recrystallizing the solid obtained from heptane, 10.6 g (81%yield) of a pale yellow powder of the desired compound are obtained.

[0189] Melting point: 114° C.

[0190] UV absorption (as a solution in ethanol):

[0191] λ_(max)=355 nm, ε_(max)=31 900, EI %=800

[0192] Elemental analysis for C₂₄H₃₄N₂O₃

[0193] calculated: C 72.33; H 8.60; N 7.03; O 12.04

[0194] found: C 72.40; H 8.55; N 7.10; O 12.28

EXAMPLE 5

[0195]

[0196] Preparation of 2-ethylhexyl2-cyano-3-[4-(2-ethyl-hexanoyl)aminophenyl]acrylate

[0197] 10 g (0.033 mol) of 2-ethylhexyl3-(4-aminophenyl)-2-cyanoacrylate prepared in accordance with step a) ofExample 4 are dissolved in 50 ml of tetrahydrofuran.

[0198] 5.4 9 (0.033 mol) of 2-ethylhexanoyl chloride are added dropwisethereto at room temperature, resulting in a slight temperature increase.The reaction mixture is heated to 45° C. and 3.3 g (0.033 mol) oftriethylamine are then added. Heating of the mixture is continued on awater bath for 1 hour 30 minutes. After cooling to room temperature, 150ml of water are added and the resulting mixture is extracted withdichloromethane and evaporated to dryness. The yellow solid obtained isrecrystallized from heptane and 10.8 g (77% yield) of the desiredcompound are obtained in the form of a pale yellow powder.

[0199] Melting point: 68° C.

[0200] UW absorption (as a solution in ethanol):

[0201] λ_(max)=353 nm, ε_(max)=34 300, EI %=804

[0202] Elemental analysis for C₂₆H₃₈N₂O₃

[0203] calculated: C 73.20; H 8.98; N 6.57; O 11.25

[0204] found: C 73.43; H 8.86; N 6.68; O 11.45

EXAMPLE 6

[0205]

[0206] a) Preparation of ethyl 3-(4-acetylaminophenyl)-2-cyanoacrylate

[0207] A mixture of 33.9 g (0.3 mol) of ethyl cyanoacetate and 59.1 9(0.3 mol) of 4-acetamidobenzaldehyde in 300 ml of ethanol in thepresence of 5 ml of piperidine is refluxed for 3 hours. The very viscousmedium is diluted with 800 ml of hot ethanol. It is filtered while hot.The yellow solid obtained is washed with hot ethanol. After filtrationand drying, 32 g (41% yield) of ethyl3-(4-acetylaminophenyl)-2-cyanoacrylate are obtained in the form of apale yellow powder.

[0208] Melting point: 187° C.

[0209] UV absorption (as a solution in ethanol):

[0210] λ_(max)=350 nm, ε_(max)=31 820, EI %=1 232

[0211] Elemental analysis for C₁₄H₁₄N₂O₃

[0212] calculated: C 65.11; H 5.46; N 10.85; O 18.58

[0213] found: C 64.89; H 5.63; N 11.06; O 18.38

[0214] b) Preparation of 2-trimethylsilylethyl3-[4-acetyl-aminophenyl]-2-cyanoacrylate

[0215] 2 g (0.0078 mol) of ethyl 3-(4-acetylaminophenyl)-2-cyanoacrylatein 20 ml of 2-trimethylsilylethanol containing 0.1 ml of piperidine arerefluxed (150° C.) for 3 hours.

[0216] The large excess of 2-trimethylsilylethanol is evaporated off atnormal pressure. After cooling to room temperature, 50 ml of heptane areadded to the residue. The yellow solid obtained after triturating inheptane is filtered off, washed with heptane and dried. 2.1 g (78%yield) of the desired compound are obtained in the form a pale yellowpowder.

[0217] Melting point: 136° C.

[0218] UV absorption (as a solution in ethanol):

[0219] λ_(max)=349 nm, ε_(max)=27 450, EI %=830

[0220] Elemental analysis for C₁₇H₂₂N₂O₃Si

[0221] calculated: C 61.79; H 6.71; N 8.48; Si 8.50

[0222] found: C 61.40; H 6.80; N 8.36; Si 8.15

EXAMPLE 7

[0223]

[0224] Preparation of the 2-ethylhexyl2-cyano-3-[4-(acetyl-aminophenyl]acrylate dimer

[0225] 6 g (0.02 mol) of 2-ethylhexyl 3-(4-aminophenyl)-2-cyanoacrylatesynthesized in step a) of Example 4 are dissolved in 60 ml oftetrahydrofuran. 1.6 g (0.01 mol) of succinyl chloride are addeddropwise at room temperature, resulting in a temperature increase to 36°C. The mixture is heated to about 45° C. and 2.02 g (0.02 mol) oftriethylamine are then added. The resulting mixture is heated at 55° C.for 3 hours. The reaction medium, which has become viscous, is cooled toroom temperature and filtered. It is washed thoroughly with water,suction-filtered thoroughly and then washed with a minimum amount of 96%ethanol. After drying the solid obtained, 4.6 g (67% yield) of a paleyellow powder of the desired compound are obtained.

[0226] Melting point: 235° C.

[0227] UV absorption (as a solution in ethanol):

[0228] λ_(max)=356 nm, ε_(max)=62 620, EI %=917

[0229] Elemental analysis for C₂₄H₃₄N₂O₃, ½ H₂O

[0230] calculated: C 69.44; H 7.43; N 8.10; O 15.03

[0231] found: C 69.71; H 7.39; N 8.36; O 15.01

EXAMPLE 8

[0232]

[0233] a) Preparation of 3-trimethylsilylpropanoyl chloride

[0234] 13.5 g (0.11 mol) of thionyl chloride are added dropwise withstirring to a mixture of 10 9 (0.068 mol) of 3-trimethylsilylpropanoicacid in 30 ml of 1,2-di-chloroethane. The reaction mixture is heated at40° C. for 2 hours. The excess thionyl chloride is removed bydistillation under reduced pressure. The solution obtained is usedwithout further purification for the following step.

[0235] b) Preparation of ethyl2-cyano-3-[4-(3-trimethyl-silylpropanoylamino)phenyl]acrylate

[0236] A suspension of 13.7 g (0.0633 mol) of ethyl3-(4-aminophenyl)-2-cyanoacrylate prepared in accordance with step a) ofExample 1 in 80 ml of 1,2-dichloroethane is introduced portionwise atroom temperature into the solution obtained above. The heterogeneousreaction mixture is heated to 40° C. and 7.1 g (0.07 mol) oftriethylamine are then added dropwise. Heating is continued at between45 and 50° C. for 1 hour. After cooling to room temperature, thereaction mixture is poured into 500 ml of water. The organic phase isseparated out, washed twice with water and dried over sodium sulphate,and the solvent is evaporated off. The solid obtained is recrystallizedfrom 1,2-dichloroethane and 8.5 g (40% yield) of the desired compoundare obtained in the form of a pale yellow powder.

[0237] Melting point: 157° C.

[0238] UV absorption (as a solution in ethanol):

[0239] λ_(max)=352 nm, ε_(max)=30 730, EI %=892

[0240] Elemental analysis for C₁₈H₂₄N₂O₃Si

[0241] calculated: C 62.76; H 7.02; N 8.13; O 8.15

[0242] found: C 62.84; H 7.06; N 8.16; O 7.93

EXAMPLE 9

[0243]

[0244] Preparation of ethyl2-cyano-3-[4-(2-ethylhexyloxy-carbonylamino)phenyl]acrylate

[0245] 4.3 g (0.02 mol) of ethyl 3-(4-aminophenyl)-2-cyano-acrylateprepared in accordance with step a) of Example 1 are dissolved in 50 mlof tetrahydrofuran.

[0246] 3.8 g (0.02 mol) of 2-ethylhexyl chloroformate are added dropwisethereto at room temperature, followed by addition of 2.02 g (0.02 mol)of triethylamine. The mixture is heated at 50° C. on a water bath for 2hours. After cooling to room temperature, 100 ml of water are added, theresulting mixture is extracted with dichloromethane and the extracts areevaporated to dryness. The residue is again extracted with ethyl ether.The paste obtained is chromatographed on silica (eluent:dichloromethane). The fractions containing the desired compound arecombined. After evaporation, an oil that crystallizes is obtained. Thesolid obtained is recrystallized from heptane and 2.2 9 (44% yield) ofthe desired compound are obtained in the form of a pale yellow powder.

[0247] Melting point: 105° C.

[0248] UV absorption (as a solution in ethanol):

[0249] λ_(max)=355 nm, ε_(max)=31 860, EI %=856

[0250] Elemental analysis for C₂₁H₂₈N₂O₄

[0251] calculated: C 67.72; H 7.58; N 7.52; O 17.18

[0252] found: C 67.78; H 7.45; N 7.81; O 17.05

EXAMPLE 10

[0253] Antisun Composition (Oil-in-Water Emulsion) 2-ethylhexyl3-(4-acetylaminophenyl)- 4 g 2-cyanoacrylate (compound of Example 2)80/20 mixture of cetylstearyl alcohol and 7 g of oxyethylenated (33 molof EO) cetyl- stearyl alcohol, sold by the company Tensia under thetrade name Dehsconet ® 390 mixture of glyceryl monostearate and 2 gdistearate, sold under the trade name Cerasynth ® SD by the company ISPCetyl alcohol 1.5 g polydimethylsiloxane sold under the name 1.5 g DC200 Fluid ® by the company Dow Corning C₁₂₋₁₅ alkyl benzoate, sold underthe name 16 g Finsolv ® TN by the company Finetex glycerol 20%preserving agents qs demineralized water qs 100 g

[0254] The sunscreen and the surfactants are dissolved in the fattyphase heated to about 70-80° C. The water heated to the same temperatureis then added with vigorous stirring. Stirring is continued for 10 to 15minutes, the mixture is then allowed to cool with moderate stirring toabout 40° C. and the preserving agents are added. An antisun cream thatis particularly effective against UV-A and that does not stain thesubstrates with which it is placed in contact is thus obtained.

1. Cosmetic composition for topical use, in particular intended forphotoprotecting the skin and/or the hair, containing, in a cosmeticallyacceptable support, at least one compound of formula (1) or (2)

in which X₁ represents a radical R₃—(C═O)—, R₃—SO₂— or R₃—O—(C═O)—, X₂represents a divalent radical of formula —(C═O)—R′₃—(C═O)—,—SO₂—R′₃—SO₂— or —(C═O)—O—R′₃—O—(C═O)—, Y represents a radical —(C═O)—R₄or —SO₂R₅, R₂ represents a linear or branched C₁₋₈ alkyl group, n is 0,1 or 2, R₃ represents a linear or branched C₁₋₃₀ alkyl or C₃₋₃₀ alkenylradical, possibly bearing one or more hydroxyl substituents and possiblycontaining, in the carbon chain, one or more hetero atoms chosen fromoxygen, nitrogen and silicon atoms, R′₃ represents a single bond or alinear or branched divalent C₁₋₃₀ alkylene or C₃₋₃₀ alkenylene radical,possibly bearing one or more hydroxyl substituents and possiblycontaining, in the carbon chain, one or more hetero atoms chosen fromoxygen, nitrogen and silicon atoms, R₄ represents a radical —OR₆ or—NHR₆, R₅ represents a linear or branched C₁₋₃₀ alkyl radical or aphenyl nucleus that is unsubstituted or substituted with C₁₋₄ alkyl oralkoxy radicals, R₆ represents a linear or branched C₁₋₃₀ alkyl or C₃₋₃₀alkenyl radical, possibly bearing one or more hydroxyl substituents andpossibly containing, in the carbon chain, one or more hetero atomschosen from oxygen, nitrogen and silicon atoms.
 2. Cosmetic compositionaccording to claim 1, characterized in that X₁ represents a radicalR₃—(C═O)— or R₃—O—(C═O)—, X₂ represents a radical —(C═O)—CH₂—CH₂—(C═O)—,Y represents a radical —(C═O)—R₄, n is 0, R₃ represents a linear orbranched C₁₋₁₀ alkyl radical, R₄ represents a radical —O—R₆, and R₆represents a linear or branched C₁₋₃₀ alkyl radical optionallycontaining one or more silicon atoms.
 3. Cosmetic composition accordingto claim 1 or 2, characterized in that the compound(s) of formula (1) or(2) is(are) present in a proportion of from 0.1% to 20% by weight andpreferably in a proportion of from 0.5% to 10% by weight relative to thetotal weight of the cosmetic composition.
 4. Cosmetic compositionaccording to any one of the preceding claims, characterized in that italso contains one or more organic sunscreens that are active in the UV-Aand/or UV-B range, other than those of formula (1) or (2).
 5. Cosmeticcomposition according to claim 4, characterized in that the organicsunscreens that are active in the UV-A and/or UV-B range, other thanthose of formulae (1) and (2), are chosen from salicylic derivatives,benzylidenecamphor derivatives, triazine derivatives, benzophenonederivatives, cinnamic derivatives, β,β′-diphenylacrylate derivatives,phenylbenzimidazole derivatives, anthranilic derivatives, imidazolinederivatives, methylenebis(hydroxyphenylbenzotriazole) derivatives,p-aminobenzoic acid derivatives, screening hydrocarbon polymers andscreening silicones.
 6. Cosmetic composition according to claim 5,characterized in that the organic sunscreens that are active in the UV-Aand/or UV-B range, other than those of formulae (1) and (2), are chosenfrom the following: ethylhexyl salicylate, ethylhexyl methoxycinnamate,octocrylene, phenylbenzimidazolesulphonic acid,terephthalylidenedicamphorsulphonic acid, benzophenone-3,benzophenone-4, benzophenone-5, 4-methylbenzylidenecamphor,benzimidazilate, anisotriazine, ethylhexyltriazone,diethylhexylbutamidotriazone,methylenebis(benzotriazolyl)tetramethylbutylphenol,drometrizoletrisiloxane, and mixtures thereof.
 7. Cosmetic compositionaccording to any one of the preceding claims, characterized in that italso contains one or more mineral pigments chosen from nanopigments ofmetal oxides such as titanium oxide, iron oxide, zinc oxide, zirconiumoxide and cerium oxide, that are optionally coated, and mixturesthereof.
 8. Cosmetic composition according to any one of the precedingclaims, characterized in that it also contains at least one agent forartificially tanning and/or browning the skin.
 9. Cosmetic compositionaccording to any one of the preceding claims, characterized in that italso contains one or more adjuvants chosen from fatty substances,organic solvents, thickeners, antioxidants, opacifiers, stabilizers,antifoams, fragrances, preserving agents, fillers, sequestering agents,propellants, pH regulators, colorants, and cosmetic active principles.10. Cosmetic composition for protecting the skin against UV rays,according to any one of the preceding claims, characterized in that itis in the form of a lotion, a suspension, a dispersion, an emulsion, agel, a cream-gel, an ointment, a solid tube, an aerosol mousse or aspray.
 11. Cosmetic composition for protecting the hair against UV rays,according to any one of claims 1 to 9, characterized in that it is inthe form of a shampoo, a lotion, a gel, a rinse-out composition, astyling or treating lotion or gel, a blow-drying or hairsetting lotionor gel, a permanent-waving, straightening, dyeing or bleachingcomposition for the hair or a hair lacquer.
 12. Cosmetic composition formaking up the eyelashes, the eyebrows, the skin or the hair according toany one of claims 1 to 9, characterized in that it is in the form of anepidermal treatment cream, a foundation, a tube of lipstick, aneyeshadow, a face powder, a mascara, an eyeliner or a colouring gel. 13.Compound of formula (2)

in which X₂ represents a divalent radical of formula —(C═O)—R′₃—(C═O)—,—SO₂—R′₃—SO₂— or —(C═O)—O—R′₃—O—(C═O)—, Y represents a radical —(C═O)—R₄or —SO₂R₅, R₂ represents a linear or branched C₁₋₈ alkyl group, n is 0,1 or 2, R′₃ represents a single bond or a linear or branched divalentC₁₋₃₀ alkylene or C₃₋₃₀ alkenylene radical, possibly bearing one or morehydroxyl substituents and possibly containing, in the carbon chain, oneor more hetero atoms chosen from oxygen, nitrogen and silicon atoms, R₄represents a radical —OR₆ or —NHR₆, R₅ represents a linear or branchedC₁₋₃₀ alkyl radical or a phenyl nucleus that is unsubstituted orsubstituted with C₁₋₄ alkyl or alkoxy radicals, R₆ represents a linearor branched C₁₋₃₀ alkyl or C₃₋₃₀ alkenyl radical, possibly bearing oneor more hydroxyl substituents and possibly containing, in the carbonchain, one or more hetero atoms chosen from oxygen, nitrogen and siliconatoms.
 14. Non-therapeutic process for protecting the skin and/or thehair against solar radiation, characterized in that it consists inapplying to the skin and/or the hair an effective amount of a cosmeticcomposition according to any one of claims 1 to 12.